1. Field of the Invention
The present invention relates to the stabilization of Mn(II), Mn(III), Mn(IV), and Mn(VII) on solid supports, and to the use these solid supported oxidation states of Mn in various industrial applications.
2. Description of the Prior Art
The metallic element manganese, (Mn), in its various forms, is presently used in a variety of industrial settings. For example, KMnO4-coated zeolites have been used in the removal of mercaptans and other malodorous compounds from the environment. Odor removal or neutralization has become increasing important in the modern industrialized environment, due at least in part to the increased production and widespread use of industrial chemicals. Many of these chemicals have disagreeable odors that are unbearable to human beings. Depending on their chemical characteristics and intensity, these odors can be a nuisance or cause adverse health effects particularly if exposure to them is prolonged. Often these health effects are non-specific symptoms, i.e., headaches, nausea, reflex nausea, gastrointestinal (G.I.) distress, fatigue, eye irritation, throat irritation, shortness of breath, runny nose, sleep disturbance, inability to concentrate, classical stress response, etc., which may or may not be directly linked to a specific chemical or exposure event. Therefore, a need exists to remove these malodors both for aesthetic and/or health reasons.
In the discussion which follows, odor removal is used as one example to explain the utility of the compositions and method of the present invention. In order to explain the benefits obtained by the methods and compositions of the invention, it is instructive to classify some malodors based upon their chemistry. These malodors are usually classified into three types: 1) aliphatic acids, 2) amines, and 3) sulfur compounds.
The odor of aliphatic acids is sharp and irritating, resembling formic and acetic acid but unique to butyric, valeric, and caproic acid. The higher acids have negligible odor due to their low volatility.
Aromatic amines are generally very toxic and readily adsorbed through the skin, often with fatal results. Methylamines and ethylamines smell more like ammonia, whereas higher alkylamines have a fishy odor.
Major sources of organosulfur compounds in the atmosphere are microbial degradation, wood pulping, starch manufacturing, sewage treatment, poultry processing wastes (e.g., methionine and cysteine, S-containing amino acids), and petroleum refining. Methanethiol and other light alkylthiols are fairly common air pollutants that have “ultragarlic” odors. Gaseous methanethiol and volatile liquid ethanethiol are used as odorant leak detecting additives for natural gas, propane, and butane and are employed as intermediates in pesticide synthesis. The substitution of alkyl or aryl hydrocarbon groups such as phenyl and methyl for H on H2S leads to mercaptans (R—SH) and thioesters (R—S—R).
Due to the intensely foul odor of mercaptans, considerable research is being directed towards the removal of these compounds in a safe and efficient manner. Commonly reported methods of removing mercaptans employ the use of an oxidation reagent, including diatomic oxygen, ozone, hydrogen peroxide, and various metal permanganates (Hudlicky, 1990). In most of these cases, the mercaptans are oxidized to the disulfides or sulfonic acids, considerably less malodorous compounds. For example, the oxidation of 2-mercaptoethanol to the disulfide with oxygen in the presence of Co(II)-4,4′,4″,4′″-tetrasulfophthalocyanine (CoTSP) has been reported as shown in the following equation (Leung and Hoffman, 1988): 
Areas of particular concern for mercaptan removal include industrial waste water treatment as well as municipal drinking water treatment. The majority of chemical oxidants are relatively expensive. The presence of high concentrations of mercaptans, particularly in various industrial waste water streams, and the likelihood of increasingly strict environmental regulations makes the search for more efficient and inexpensive oxidants a significant priority.
Several technologies have been proposed for the removal of malodors depending upon the particular chemistry involved. For example, materials that contain Lewis acid sites (i.e., H-ZSM-5, alumina, MnO2, etc) can efficiently remove amine-based malodors. However, sulfur-containing malodors have only been successfully removed using oxidants and removal by C has been documented in the literature (see below).
The following materials are currently being used in industrial applications with the noted limitations:    (1) Activated carbon/saw dust/fiber-coated with MnO2:
Activated carbon/saw dust/fiber coated with MnO2 has been used to remove mercaptan odors (Turk et al., 1973; Sarkkinen, 1990; Yoshida et al., 1992; Vempati 2002). The fibers generally used are Zn phosphate or ZnS doped with Mn (Iannicelli, 1990; Yamamoto et al., 1991; Hirukawa et al., 1998). Increase in humidity and/or temperature can decrease the effectiveness of the activated carbon and saw dust due to a decrease in available surfaces for reaction. Furthermore, the instability of activated C at high temperature may reduce its activity.
Vempati (2002) has demonstrated the removal of mercaptan odor using >3% amorphous C present in the rice hull ash. However rice hull ash with >10% amorphous C worked best. (Vempati, R. K. 2002. Composition and Method of Forming Siliceous Ash From Siliceous Waste Material, U.S. Pat. No. 6,444,186).    (2) MnO2:
MnO2 has been used for the removal of malodors. (Mitrofanov et al., 1969; Cvjeticanin et al., 1982; Iannicelli et al., 1985; Lutz et al., 1986; Futomi et al., 1990; Iannicelli, 1990; Tetsuya and Shigeo, 1990; Hideo et al., 1991; Yoshimitsu, 1991; Norikazu et al., 1992; Masahiro, 1994; Kimiyasu et al., 1996; Mazgarov et al., 1997; Sasaki et al., 1997; Chu and Wu, 1998; Honda et al., 1998; Firouzabadi et al., 1999). In the above studies, amine odors were removed at room temperature but the removal of sulfides and mercaptan odors required either an oxidant or high temperature (in the range of 100 to 400° C.).    (3) KMnO4-coated zeolites:
Potassium permanganate (KMnO4)-coated zeolites/clays/fibers have been used for the preservation and deodorization of flowers, fruits and vegetables; stench prevention in sludges, sewages and industrial wastewater; asphalt treatment plant and food processing, and removal of mercaptans in oil and gas (Behrens, 1933; Kostrikov et al., 1978; Imafuku et al., 1979; Botkin et al., 1981, Tiwari and Verma, 1983; Yoshioka and Tanaka, 1987; Kobayashi et al., 1987; Kawamoto et al., 1989; Sarkkinen, 1990; Imamura and Imose, 1992; England, 1995; Firouzabadi et al., 1989, Yaide, 2001; Handa and Yasuhiro; 2002). The preservation of the horticultural crops was by degradation of the ethylene gas released, and maintenance of the moisture and atmospheric composition (Saburu, 1980; Paulo, 2000).    (4) H2O2 process:
Sulfur-containing compounds are oxidized by H2O2 to various products depending on the pH and catalyst (Equations 2-5). Mercaptans can be converted to disulfides (Equation 2) or sulfonic acids (Equation 3). Sulfides are converted to sulfoxides (Equation 4), while disulfides are converted to sulfonic acids under strongly acidic conditions (Equation 5). 
The use of H2O2 may not be feasible in reactions involving gases and organic solvents. Furthermore, H2O2 is hazardous and fairly expensive.
Applicant's invention is directed toward a process for the production of Mn(II), Mn(III) and Mn(VII) in stabilized oxidation states on solid supports, and to the use these solid supported oxidation states of Mn in various industrial applications such as odor removal. Applicant is unaware at this time of any relevant prior art processes for producing solid supported Mn(II), Mn(III) or Mn(VII). There is little to no information in the literature regarding the stability of solid supported Mn(III) and Mn(VII).